JPH1180616A - Antimicrobial coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antimicrobial coating which possesses excellent durability of antimicrobial activity, discoloration resistance and other properties by incorporating a polymeric material contg. a hydrophilic material into an antimicrobial coating contg. a phosphonium salt compd. SOLUTION: This antimicrobial coating comprises a phosphonium salt compd. pref. having a functional group chemically bondable to a polymeric material (e.g. a compd. of the formula) and/or a polymeric material contg. the phosphonium salt compd., pref. with the phosphonium salt compd. being bonded to the main chain or side chain thereof (e.g. a polyester composed mainly of a dicarboxylic acid moiety and a glycol moiety, the polyester having been copolymerized with 1 to 50 mol.% compd. of formula), wherein a hydrophilic material pref. having a functional group chemically bondable to a polymeric material and/or a polymeric material contg. the hydrophilic material (e.g. a hydrophilic polymer copolymerized with a polymer contg. a phosphonium salt compd.). In the formula, A represents an arom. group; X1 and X2 each represent an ester-forming functional group; and R1 to R4 each represent an alkyl, provided that one or more of R1 to R4 represents a 10-20C alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial coating comprising a polymer substance having a phosphonium base, and more particularly to an antibacterial coating capable of providing a coating film having excellent antibacterial properties without discoloring with time. , Film, sheet, fiber, molded products such as plastic, paper, wood, ceramic,
The present invention relates to an antibacterial paint suitable for use in cement, glass, metal plates and the like.

[0002]

2. Description of the Related Art The occurrence of bacteria and mold on painted surfaces inside and outside a building has been a problem, and various antibacterial materials and resin compositions and paints containing the same have been studied. Many of the antibacterial materials currently mainly studied or used are chitin, chitosan, wasabi extract, mustard extract, hinokitiol, natural products such as tea-extracted polyphenols, photooxidation catalyst titanium oxide particles, zinc oxide ultrafine particles,
Inorganic compounds such as silver-containing zeolite and silver-containing zirconium phosphate, and organic synthetic products such as organic ammonium salt-based and organic phosphonium salt-based compounds are used. Natural products and inorganic products represented by silver have recently been receiving attention as being safe in terms of toxicity. For example, a zeolite supporting a metal ion having an antibacterial action (Japanese Patent Laid-Open No. 60-2021)
A number of paints have been proposed, including inorganic antibacterial agents such as phosphate compounds having the same metal ion (for example, JP-A-5-59308). However, silver ions, which are the mainstream of inorganic antibacterial agents, are supported on inorganic compound carriers, and silver ions are often eluted and the antibacterial properties are reduced, especially in places exposed to water in a relatively short time. There is a problem that disappears, and when mixed with resin or paint, there are many things that color or discolor it,
This significantly impaired the design of products or painted products obtained from resins or paints containing the same. On the other hand, organic synthetic products generally have better antibacterial and antifungal properties than natural products and inorganic products, but antibacterial components tend to volatilize and separate easily, and are often avoided because of their toxicity. This is because the antibacterial component is easily dissolved in water, an organic solvent, or the like. Recently, an insoluble, nontoxic, immobilized antibacterial agent has been developed.
There is the following disclosure example as this improvement method.

Japanese Patent Application Laid-Open No. 54-86584 discloses an antibacterial agent mainly composed of a polymer substance containing an antibacterial agent component having a quaternary ammonium base ionically bonded to an acidic group such as a carboxyl group or a sulfonic acid group. Materials are described. JP-A-61-245378 describes a fiber comprising a polyester copolymer containing an antibacterial agent component having a basic group such as an amidine group or a quaternary ammonium group.

JP-A-57-204286, 63-609
030, 62-114903, JP-A-1-93596,
According to Japanese Unexamined Patent Publication No. 24090/1990, phosphonium salt compounds, as well as various nitrogen-containing compounds, are known as biologically active chemicals having a broad spectrum of activity against bacteria. There is disclosed an invention in which the above phosphonium salt is immobilized on a polymer substance to attempt to expand its use.

JP-A-4-266912 discloses a phosphonium salt-based vinyl polymer antibacterial agent.
814365 discloses a vinylbenzylphosphonium salt-based vinyl polymer antibacterial agent. Further, JP-A-5-310820 describes an antibacterial material mainly composed of a polymer substance containing an antibacterial component having an acidic group and a phosphonium base ionically bonded to the acidic group. In that example, a polyester using a phosphonium salt of sulfoisophthalic acid is disclosed. The present inventors have disclosed Japanese Patent Application Laid-Open No. Hei 4-266912,
814365, Japanese Patent Application Laid-Open No. 5-310820, and after examining the examples, synthesizing a phosphonium base-containing vinyl polymer and a copolyester and a coating material using the same, applying it to the structure forming body, However, the antibacterial activity was insufficient, and it was necessary to improve the antibacterial material.

Further, even if an attempt is made to bond trinormal butyldodecylphosphonium base to the polyester in an amount of 50 mol% or more in order to improve the antibacterial property, the coloring of the polymer and the reduction of the mechanical properties due to the reduction of the glass transition point become remarkable. In addition, there has been a problem that sufficient antibacterial properties cannot be obtained.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have solved the above problems and have provided an antibacterial paint which improves the antibacterial property while maintaining an appropriate amount of phosphonium base which is an antibacterial component in a polymer substance. With the goal.

[0008]

In order to achieve the above object, the antibacterial paint of the present invention comprises a phosphonium salt compound and / or
Alternatively, in the antibacterial paint containing the polymer substance containing the phosphonium salt compound, the antibacterial paint contains a hydrophilic substance and / or a polymer substance containing the hydrophilic substance.

The antibacterial paint of the present invention having the above constitution is characterized in that its antibacterial activity is remarkably enhanced. In this case, the phosphonium salt compound can have a functional group capable of chemically bonding to the polymer substance. The antibacterial paint of the present invention having the above configuration is characterized in that it has excellent antibacterial durability after the formation of a coating film. In this case, the phosphonium salt compound may contain an acidic group and a phosphonium base ionically bonded to the acidic group. The antibacterial paint having the above configuration has excellent heat resistance. In this case, a polymer substance having a phosphonium salt compound bonded to a main chain or a side chain can be contained as an active ingredient.

[0010] The antibacterial paint having the above constitution has excellent durability of the antibacterial property after the formation of the coating film. In this case,
The high-molecular polymer contains a dicarboxylic acid and a glycol component as main components, and a phosphonium salt of a sulfonic acid group-containing difunctional aromatic compound represented by the following chemical formula (1) in an amount of 1 to 50 mol% in all dicarboxylic acids. It can be a polymerized copolyester.

[0011]

Embedded image

(Chemical formula 2 is the same as chemical formula 1;
Is an aromatic group, X ₁ and X ₂ are ester-forming functional groups,
R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups, at least one of which is an alkyl group having 10 to 20 carbon atoms)

The antibacterial coating composition of the present invention having the above-mentioned structure has structurally stable and good thermal and mechanical properties, and can be used for various applications. In this case,
The hydrophilic substance may have a functional group capable of chemically bonding to the polymer substance. The antibacterial paint of the present invention having the above-described structure further enhances the antibacterial performance and has excellent durability of the antibacterial property. In this case, the active ingredient may be dispersed or dissolved in an aqueous solvent and / or an organic solvent. The antibacterial paint having the above structure can be applied to various structure forming bodies to maintain the antibacterial property.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the antibacterial paint of the present invention will be described in detail. The antibacterial paint of the present invention is an antibacterial paint containing a phosphonium salt compound and / or a polymer substance containing the phosphonium salt compound, and has, for example, a functional group capable of forming a chemical bond with the polymer substance. Examples thereof include a phosphonium salt compound and a polymer in which the phosphonium salt compound is bonded to a main chain or a side chain. Examples of the phosphonium salt compound having a functional group capable of forming a chemical bond with a polymer substance include a carboxyl group,
Derivatives such as acidic groups such as sulfonic acid groups and phosphonic acid groups or salts thereof, compounds having halogen ions such as hydroxyl group, alkoxyl group, amino group, epoxy group, fluorine, chlorine, bromine and iodine, acrylic acid, acrylamide Various acrylic compounds such as, isocyanate compounds,
Compounds obtained by introducing a phosphonium base into a compound having an unsaturated double bond such as fumaric acid and maleic acid are exemplified. One example is a phosphonium salt of a sulfonic acid group-containing bifunctional aromatic compound represented by the following chemical formula (1). These phosphonium salt compounds can form a chemical bond with a polymer substance in an antibacterial paint or in a process of forming a coating film using the antibacterial paint. The polymer substance containing a phosphonium salt compound may be a mixture of the phosphonium salt compound as a monomer in the polymer substance, or a copolymer of the phosphonium salt compound with the polymer substance. Preferred examples of the polymer material containing a phosphonium salt compound include a phosphonium salt of a sulfonic acid group-containing bifunctional aromatic compound having a dicarboxylic acid component and a glycol component as main components and represented by the above formula (1). Copolymerized polyesters obtained by copolymerizing 1 mol% to 50 mol% in dicarboxylic acid are exemplified. Such a copolyester has a remarkable effect of improving antibacterial properties by having a hydrophilic substance bonded by a chemical bond.

Examples of R ₁ , R ₂ , R ₃ and R ₄ of the phosphonium salt compound of the sulfonic acid group-containing bifunctional aromatic compound (Chem. 1) constituting such a copolymerized polyester include methyl, ethyl , Propyl, butyl, pentyl, hexyl, peptyl, octyl, dodecyl, pentadecyl, hexadecyl, octadecyl and the like, and at least one of R ₁ , R ₂ , R ₃ , and R ₄ is carbon. An alkyl group of several tens to 20 is preferable from the viewpoint of maximizing the antibacterial effect. Preferred examples of X include, in addition to acid groups such as a carboxyl group, a sulfonic acid group and a phosphonic acid group, and derivatives such as salts thereof, a hydroxyl group, an alkoxyl group, an amino group, an epoxy group, fluorine, chlorine, bromine, And halogen ions such as iodine.

Specific examples of the dicarboxylic acid component constituting the copolymerized polyester include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and heterocyclic dicarboxylic acids. As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, phthalic acid, 2,6-
There are naphthalenedicarboxylic acid, 4,4-dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane and derivatives thereof, and alicyclic dicarboxylic acids include cyclohexane-1,4-dicarboxylic acid and derivatives thereof. Adipic acid as the aromatic dicarboxylic acid,
Sebacic acid, dodecanedioic acid, eicosandioic acid,
There are dimer acids and their derivatives, and the heterocyclic dicarboxylic acids include pyridine carboxylic acids and their derivatives. In addition to such a dicarboxylic acid component, it is also possible to include oxycarboxylic acids such as p-oxybenzoic acid and polyfunctional acids such as trimellitic acid, pyromellitic acid and derivatives thereof.

The glycol component includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexane Examples include dimethanol, an ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. In addition, it may contain a small amount of a compound containing an amide bond, urethane bond, ether bond, carbonate bond or the like.

Examples of the phosphonium salt of a sulfonic acid group-containing bifunctional aromatic compound include tri-n sulfoisophthalic acid.
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoisophthalate, tri-n-butylhexadecylphosphonium sulfoisophthalate, tri-n-butyltetradecylphosphonium sulfoisophthalate, tri-n sulfoisophthalate -Butyl dodecyl phosphonium salt, tri-n-sulfoterephthalate
-Butyldecylphosphonium salt, tri-n-butyloctadecylphosphonium sulfoterephthalate, tri-n-butylhexadecylphosphonium sulfoterephthalate, tri-n-butyltetradecylphosphonium sulfoterephthalate, tri-n sulfoterephthalate -Butyl dodecyl phosphonium salt, 4-sulfonaphthalene-2,
7-dicarboxylic acid tri-n-butyldecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyloctadecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butylhexa Decylphosphonium salt, 4-sulfonaphthalene-
2,7-dicarboxylic acid tri-n-butyltetradecylphosphonium salt, 4-sulfonaphthalene-2,7-dicarboxylic acid tri-n-butyldodecylphosphonium salt, and the like. In terms of antibacterial activity, trisulfoisophthalate is preferred. −
n-butylhexadecylphosphonium salt, tri-n-butyltetradecylphosphonium sulfoisophthalate,
Tri-n-butyldodecylphosphonium sulfoisophthalate is particularly preferred.

The above-mentioned phosphonium salts of aromatic dicarboxylic acids include aromatic dicarboxylic acids or their sodium, potassium, and ammonium salts, tri-n-butylhexadecylphosphonium bromide, tri-n-butyltetradecylphosphonium bromide, and tri-n-butyltetradecylphosphonium bromide. It can be obtained by reacting a phosphonium salt such as n-butyldodecylphosphonium bromide.

The reaction solvent is not particularly limited, but water is most preferred. For the purpose of improving heat resistance so that the copolymerized polyester does not have coloration and gel generation, magnesium acetate, magnesium salts such as magnesium chloride, calcium acetate, calcium salts such as calcium chloride, manganese acetate, manganese chloride and the like. 20 ppm or more and 300 ppm or less of each manganese salt as a metal ion, and 20 ppm or more of phosphoric acid or a phosphate ester derivative such as trimethyl phosphate or triethyl phosphate as a P atom.
It is also possible to add up to 00 ppm. If the metal ion exceeds 300 ppm, the coloring of the polymer becomes remarkable. If it is less than 20 ppm, no improvement in the heat resistance of the polymer is observed. Further, in terms of heat resistance of the antibacterial paint, the molar ratio of the P to the metal ion (Equation 1) is 0.4 to 0.4.
It is preferably 1.0.

[0021]

(Equation 1)

When the molar ratio of P to the metal ion is less than 0.4 or more than 1.0, the coloring of the polymer and the generation of coarse particles become remarkable, making it difficult to apply the composition as a paint. As a method for producing a copolymerized polyester which is a main component of the present invention in the above-mentioned typical example, a direct reaction between an aromatic dicarboxylic acid and a glycol, a so-called direct polymerization method, a dimethyl ester of an aromatic dicarboxylic acid and a glycol are used. An arbitrary production method such as a so-called transesterification method in which a transesterification reaction is performed can be applied. The timing of adding the metal ion, phosphoric acid and its derivative is not particularly limited, but it is preferable that the metal ion is added at the time of charging the raw materials and that the phosphoric acid is added before the polymerization reaction. Another preferred specific example of the polymer substance used in the antibacterial paint of the present invention is a phosphonium salt-based vinyl polymer represented by the following chemical formula (3).

[0023]

Embedded image

(R ₅ , R ₆ and R ₇ are a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an aryl group, an alkyl group substituted with a hydroxyl group or an alkoxy group, an aryl group Or an aralkyl group;
h represents a phenylene group, and X- represents an anion. n is an integer of 2 or more. )

Examples of R ₅ , R ₆ and R ₇ include methyl, ethyl, propyl, butyl, pentyl, hexyl,
Alkyl groups such as heptyl, octyl and dodecyl; aryl groups such as phenyl, tolyl and xylyl; aralkyl groups such as benzyl and phenyl); hydroxyl groups and alkoxyl groups; alkyl groups and aryl groups are particularly preferred. R ₅ , R ₆ and R ₇ may be the same group or different groups. X- is an anion, for example, a halogen ion such as fluorine, chlorine, bromine or iodine, a sulfate ion, a phosphate ion, a perchlorate ion and the like, with a halogen ion being preferred. n is not particularly limited, but is 2 to 500, preferably 10 to 300.

The antimicrobial coating composition of the present invention contains a hydrophilic substance and / or a high molecular substance containing the hydrophilic substance. The hydrophilic substance is chemically bonded to the high molecular substance in the coating component. It can be selected from a hydrophilic substance having a possible functional group, a hydrophilic substance chemically bonded to a high molecular substance, and a hydrophilic substance which itself forms a high molecular polymer. Hydrophilic substances are substances with excellent affinity for water,
It is a substance that can be dissolved, dispersed, or retained, moisturized, and swelled in water, and is a substance that, when contained in an appropriate amount, enhances the affinity between the antibacterial paint and water. Typical examples of the hydrophilic substance include organic groups containing at least one of a hydroxyl group, an amino group, an amide group, a carboxyl group or an alkali metal salt thereof, a sulfonic acid group or an alkali metal salt thereof, a quaternary ammonium base, and an amine base. There is a compound or a polymer compound, or an organic compound or a polymer compound containing at least one of a polyether chain and a polyamine chain. The polyether is a polymer compound containing two or more ether bonds in one molecule, and typically includes, for example, a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain. A polyamine is a polymer containing a basic nitrogen atom in the main chain, and typical examples include polyethyleneimine and polyalkylenepolyamine (for example, polyethylenepolyamine). By including these hydrophilic substances, the hydrophilicity of the antibacterial paint of the present invention is improved.

Specific examples of the hydrophilic substance include polyvinyl alcohol, polyacrylamide, poly (N, N-dimethylaminomethylacrylamide), poly (N, N-dimethylaminoethyl acrylate), and poly (N, N-dimethylamino). Ethyl methacrylate), polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, polyvinylimidazole, a homopolymer or copolymer of polyacrylic acid, a homopolymer or copolymer of polymethacrylic acid, a homopolymer or copolymer of maleic anhydride (eg, , Maleic anhydride-styrene copolymer), polyvinyl sulfonic acid or its copolymer or an alkali metal salt thereof, polystyrene sulfonic acid or its copolymer or their alkali metal salt, quaternary ammonium of polystyrene Salt derivatives, polyvinyl imidazoline salt, polyallylamine salt, polyethylene glycol (also known as polyethylene oxide), polypropylene glycol, polyethylene-propylene glycol, polyalkylene glycols such as polytetramethylene glycol,
Polyesters obtained by copolymerizing a polyol such as glycerin or polyglycerin or a polymer thereof, or an alkali metal salt or ammonium salt of sulfoisophthalic acid in an amount of 1 mol% to 10 mol% are exemplified.

Further, polyalkylene glycols and polyglycerols may be polyether derivatives whose terminals are blocked with alcohols, alkylphenols, fatty acids, amines, etc., for example, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyglycerin alkylene oxide adduct, Derivatives such as fatty acid esters or fatty alcohol ethers, polyglycerin fatty acid esters, polyglycerin fatty alcohol ethers, polyglycerin glycidyl ethers, and reaction products thereof can be given. Among them, polyethylene glycol, polyglycerin and derivatives thereof are preferred from the viewpoint of improving compatibility with polyester and antibacterial properties.

The molecular weight of the hydrophilic substance is not particularly limited. In the case of polyethylene glycol, the number average molecular weight is preferably 200 or more and 30,000 or less, more preferably 100 or less.
It is preferably from 0 to 25,000. The hydrophilic substance (in the case of a copolymer, it refers to a hydrophilic substance contained in the copolymer)
Although the amount of addition is not particularly limited, when polyethylene glycol is added as a hydrophilic substance, it is 0.1 to 20% by weight, preferably 0.5 to 20% by weight based on the total amount of the non-volatile components constituting the antibacterial paint. It is 10% by weight, more preferably 1 to 5% by weight. If the amount is less than 0.1% by weight, the effect of increasing the antibacterial activity is insufficient, and if it exceeds 20% by weight, the mechanical properties and the heat resistance and weather resistance of the antimicrobial composition are undesirably reduced.

The method for incorporating a hydrophilic substance into the antibacterial coating of the present invention is not particularly limited, and any method such as mixing, melt-kneading, and copolymerization can be employed. Is preferred. For example, polyesters containing the copolymerizable hydrophilic substances (monomers) such as the glycols, polyols, alkali metal salts or ammonium salts of sulfoisophthalic acid, vinylpyrrolidone, acrylic acid, styrene sulfonic acid, etc., with the phosphonium salt compound Covalent bonding to the main chain or side chain of polymers such as polyamides, polyamides, and polyolefins is effective in preventing hydrophilic substances from bleeding out of the system by effectively bonding the hydrophilic substances to those polymers. The antibacterial paint of the present invention is particularly effective for maintaining high antibacterial activity for a long period of time.

Further, a method of adding a hydrophilic substance or a monomer to the reaction system after the completion of the polymerization reaction of the polymer containing the phosphonium salt compound and mixing the polymer containing the phosphonium salt compound and the hydrophilic substance in an appropriate solvent,
For example, a method of mixing and dissolving or dispersing in water, an organic solvent such as water / alcohol mixed solvent, acetone, methyl ethyl ketone or the like, and then drying the solvent can be employed.

As another preferred example of the method for introducing a hydrophilic substance into the phosphonium salt compound-containing polymer of the present invention, a vinyl monomer having a hydrophilic group can be graft-added to the polymer. Examples of the vinyl monomer having a hydrophilic group that can be grafted onto the phosphonium salt compound-containing polymer in the present invention include those containing a carboxyl group, a hydroxyl group, a sulfonic acid group, an amide group, and the like, and can be changed to a hydrophilic group. Examples of the group include those containing an acid anhydride group, a glycidyl group, a chloro group and the like. Among them, those having a carboxyl group are most preferred.

For example, monomers containing a carboxyl group or a salt thereof such as acrylic acid, methacrylic acid and salts thereof, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, isopropyl acrylate, n
Alkyl acrylates such as -butyl acrylate and t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-
Alkyl methacrylate such as butyl methacrylate, 2
Hydroxy-containing monomers such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N -Methoxymethyl methacrylamide, N, N-dimethylolacrylamide,
Examples include amide group-containing monomers such as N-phenylacrylamide, and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate.

Other monomers having a hydrophilic group include, for example, monomers containing an epoxy group such as allyl glycidyl ether, monomers containing a sulfonic acid group or a salt thereof such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof, Monomers containing a carboxyl group or a salt thereof, such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof, and monomers containing an acid anhydride, such as maleic anhydride and itaconic anhydride. These can be used in combination with other monomers. Examples of other monomers include, for example, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl acetate, vinyl chloride, and the like. Copolymerization can be carried out using two or more kinds. The graft ratio of the vinyl group monomer having a hydrophilic group is preferably in the range of 5% to 60% by weight based on the phosphonium salt compound-containing polymer serving as the main chain.

As a method for grafting a monomer containing a hydrophilic group to the polymer containing a phosphonium salt compound, a known graft polymerization method can be used. The following method is mentioned as a typical example. For example, light,
A radical polymerization method in which radicals are generated in a main chain high molecular polymer by heat, radiation, or the like, followed by graft polymerization of a monomer, a cation polymerization method in which cations are generated using a catalyst such as AlCl ₃ or TiCl 4, or metal N
a, an anion polymerization method of generating an anion using metal Li or the like.

Further, there is a method in which a polymerizable unsaturated double bond is previously introduced into a high-molecular polymer having a main chain, and a vinyl monomer is reacted with the polymerizable unsaturated double bond. Examples of the monomer having a polymerizable unsaturated double bond used therein include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. be able to. The most preferred of these are fumaric acid, maleic acid, and 2,5-norbornene dicarboxylic acid.

Further, there is a method in which a main chain high molecular polymer having a functional group introduced into a side chain is reacted with a branch polymer having a group which reacts with the above functional group at a terminal. For example, -OH group, -SH group, -NH ₂ group, -COOH group -C
A polymer substance having a hydrogen donating group such as an ONH ₂ group, and one end having a —N ＝ C ＝ O group, a —C ＝ C ＝ O group,

[0038]

Embedded image

[0039]

Embedded image For example, a method of reacting with a vinyl polymer which is a hydrogen accepting group, and a method of reacting in a reverse combination.

In the preferred embodiment, the weight ratio of the polymer containing the phosphonium salt compound as the main chain and the vinyl monomer to be grafted is in the range of 40/60 to 95/5, more preferably 55/45 to 93 /. 7, most preferably in the range of 60/40 to 90/10. If the weight ratio of the main chain polymer is less than 40%, the graft polymerizable vinyl-based monomer remains without completely reacting, and the properties such as heat resistance and processability of the conventional polymer are impaired. When the weight ratio of the polymer in the main chain exceeds 95%, the effect of improving antibacterial properties, which is the object of the present invention, cannot be sufficiently exhibited.

The antibacterial paint of the present invention has another organic antibacterial agent or silver / zeolite particles, silver / zirconium phosphate particles, zinc oxide fine particles, and a photo-oxidation catalyst for the purpose of further improving the antibacterial activity. It is also possible to add an inorganic antibacterial agent such as titanium oxide fine particles having the following. In addition, calcium carbonate (CaCO 2) was used for the purpose of improving physical properties such as slipperiness, abrasion resistance, blocking resistance, and concealing property of the surface of a coating film obtained by using the antibacterial coating of the present invention.
₃ ), barium sulfate (BaSO ₄ ), calcium fluoride (CaF ₂ ), talc, kaolin, silicon oxide (SiO
_2), alumina (Al2O _3), titanium dioxide, zirconium oxide (ZrO _2), iron oxide (Fe ₂ O _3), inorganic particles such as alumina / silica composite oxide, crosslinked polystyrene, crosslinked polymethacrylic acid esters, crosslinked poly It is also possible to add organic particles such as acrylic acid esters.

The above particles will be described in more detail.
Calcium carbonate particles are classified into three crystal types, calcite classified into trigonal or hexagonal system, aragonite classified into orthorhombic system, and vaterite classified into hexagonal or pseudo hexagonal system, according to their crystal structures. However, any crystal type may be used, and the shape thereof may be spherical, cubic, spindle-shaped,
It can be arbitrarily selected such as a columnar shape, a needle shape, a spherical shape, and an egg shape. The kaolin particles may be of any type, whether natural kaolin, synthetic kaolin, calcinable or unburned, and the shape thereof can be arbitrarily selected, such as columnar, plate-like, spherical, spindle-like, and egg-like. Examples of the alumina include crystalline alumina hydrates such as gibbsite, bayerite, Nordstrandite, boehmite, diaspore, and todite; amorphous gels, boehmite gels, amorphous alumina hydrates such as bayerite gels, and ρ , Γ, κ, δ, θ-type intermediate activated alumina or α-type alumina. The average particle size is not particularly limited because it is necessary to change the average particle size according to the purpose.
It is preferably at least 10 μm and at most 50% by weight.
The following is preferred. When the amount of the added particles exceeds 50% by weight, the strength, stretchability and flexibility of the coating film obtained from the antibacterial coating using the same decrease.

The polymeric substance containing a phosphonium compound, which is an active ingredient of the antibacterial coating of the present invention, can be used alone as a coating, but improves the hardness, abrasion resistance, heat resistance and solvent resistance of the coating. For the purpose, another resin for forming a coating film and / or a curing agent may be used in combination. The curing reaction of the coating film forming resin and / or the curing agent may be any of a room temperature curing type, a heat curing type, a photo curing type, an ultraviolet curing type, and an electron beam curing type.

The room-temperature-curable resin for forming a coating film may be a one-component type which reacts with moisture in the atmosphere, a one-component type which reacts by adding a catalyst or a curing agent, or a two-component type, in which a crosslinking reaction is performed by mixing two components. And a two-pack type. Examples of the two-pack type include a silicone resin. Examples of the heat-curable resin for forming a coating film include acrylic resin, silicone-modified acrylic resin, polyester resin, silicone-modified polyester resin, epoxy resin, amino alkyd resin, melamine resin, guanamine resin, polyurethane resin, vinyl chloride resin, and fluororesin. Plastisol or organosol. These can be used alone or in combination of two or more.

Examples of the acrylic resin include ethylenic monomers having a hydroxyl group such as hydroxymethyl (meth) acrylate and hydroxybutyl (meth) acrylate;
Ordinary method from ethylenic monomers such as (meth) acrylic acid and crotonic acid, ethylenic monomers such as alkyl (meth) acrylate such as methyl (meth) acrylate and propyl (meth) acrylate, and monomers such as styrene And the resin polymerized in the above. In addition, the silicone-modified acrylic resin is based on 100 parts by weight of the acrylic resin, and an organic silicone (for example, -SiO as a functional group) is used.
CH ₃ , —SiOH having a number average molecular weight of 300 to 10
(Organic silicone of 00) from 5 to 50 parts by weight.

As the polyester resin, one or more polyhydric alcohols such as ethylene glycol, polyethylene glycol, butanediol, hydrogenated bisphenol A and phthalic acid, tetrahydrophthalic acid, maleic acid, succinic acid, cyclohexane-1, Resins using a basic acid such as 4-dicarboxylic acid as a raw material are exemplified. Further, the silicone-modified polyester resin can be obtained by reacting 5 to 50 parts by weight of the organic silicone with 100 parts by weight of the polyester resin.

Further, a plastisol or organosol of a vinyl chloride resin or a fluororesin can also be used. As the fluororesin, besides vinylidene fluoride resin, vinyl fluoride resin and the like, a curable fluorine paint such as fluoroolefin vinyl ether copolymer and fluoroolefin vinyl ester copolymer can be used. Examples of the curing agent include melamine resins, guanamine resins, amino resins such as urea resins, and blocked isocyanates.
Examples of the photocurable resin for forming a coating film include urethane acrylate, acrylic, epoxy, unsaturated polyester, and unsaturated melamine resins.

As the electron beam or ultraviolet curable resin, a monomer containing a polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, an epoxy group, a thiol group or the like in a molecule. Alternatively, the composition comprising the prepolymer is polymerized by ionizing radiation (electron beam, ultraviolet ray) (crosslinking reaction,
(Addition reaction and the like) and cured. Examples of the prepolymer include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, (meth) acrylate, and unsaturated polyester. Examples of the monomer include styrene-based monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentane Erythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like.

The preferred proportion of the high-molecular-weight substance containing a phosphonium salt compound as an active ingredient of the antibacterial coating of the present invention is 50 to 100 parts by weight, more preferably 60 to 90 parts by weight, based on the whole solids in the antibacterial coating. Department. When the amount is less than 50 parts by weight, the antibacterial property is not sufficiently exhibited. The preferred ratio of the phosphonium salt monomer, which is an active ingredient, contained in the antibacterial coating of the present invention is 5 to 50 parts by weight based on the total weight of other resin for forming a coating film, a curing agent and other nonvolatile solids.
When the amount is less than 5 parts by weight, the antibacterial property is not sufficiently exhibited.

The form of the antibacterial paint of the present invention includes a phosphonium salt compound and / or a polymer material containing a phosphonium salt compound as an active ingredient, a hydrophilic substance and / or a polymer substance containing a hydrophilic substance, and the like. All non-volatile components such as a film-forming resin, a curing agent, and other particles are uniformly dispersed or dissolved in an organic solvent and / or an aqueous solvent. Examples of the organic solvent include aromatic and aliphatic hydrocarbons, aliphatic alcohols, esters, ethers, and ketones. Specific examples include toluene, n-hexane, methyl ethyl ketone, isopropanol, n-butanol, ethylene glycol, propylene glycol, methyl cellosolve,
Examples include ethyl cellosolve, n-butyl cellosolve, ethyl acetate, dioxane, and tetrahydrofuran.
As the aqueous solvent, water or a mixed solvent of water and the above-mentioned organic solvent is used.

The antibacterial paint of the present invention is capable of undergoing a self-crosslinking reaction of a part of reactive groups in a polymer substance containing a phosphonium salt compound or a hydrophilic substance, which is an active ingredient thereof, in the process of forming a coating film, Interaction with a reactive group in a resin and / or a curing agent that can coexist, or between reactive groups in a resin and / or a curing agent that can coexist By having a three-dimensional cross-linked structure by cross-linking, addition polymerization and polycondensation reaction, hardness, abrasion resistance, heat resistance and solvent resistance can be improved.

The method of applying the antibacterial paint of the present invention to a substrate is not particularly limited, and a usual coating method such as air spray coating, airless coating, electrostatic coating, roll coating, curtain coating, extrusion coating and the like can be used. Can be used. The antibacterial paint of the present invention can be used in various fields requiring antibacterial properties. The intended use is not limited, but specific targets are plastic,
Examples include paper, cloth, metal, wood, glass, ceramic, cement and the like. As plastic, polyvinyl chloride,
Polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer, polyvinyl tetrafluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-4
Examples thereof include a polyfluorinated ethylene resin such as a fluorinated ethylene copolymer, polyimide, and polycarbonate. Metals include iron, aluminum, stainless steel, copper, tin, lead,
And their alloys. Examples of applications include
Paints for interior and exterior of hospitals, schools, general houses, food factories, warehouses, etc., coatings mainly for mold, such as walls, ceilings, floors, etc. of bathrooms, toilets or kitchens, plastic products with antibacterial and fungicide properties, Coatings such as wood products such as furniture, metal products such as beverage cans and pipes and the like can be given.

(Function) In the antibacterial coating material of the present invention, since the phosphonium base-containing polymer substance contains a hydrophilic group in a side chain, the antibacterial property inherent to the phosphonium base-containing polymer substance can be remarkably improved. .

(Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Hereinafter, methods for measuring the physical properties of the antibacterial paints obtained in Examples and Comparative Examples will be described.

Antibacterial Test Method S.I. diluted with 1/50 broth aureus (Staphylococcus aureus), or E. coli. 0.1 ml of a bacterium solution of Coli (Escherichia coli) (concentration: 107 cells / ml) was dropped onto a sample coated plate cut into a size of 5 cm × 5 cm, and a high-pressure steam-killed Saran wrap film was adhered thereon. Transfer the test piece to a sterile Petri dish, 37 degree (Staphylococcus aureus) or 30 degreeC
(E. coli) for 24 hours. Then, the bacteria on the sample coated plate and film were washed out with 10 ml of SCDLP medium,
It was diluted 20-fold and spread on an ordinary agar plate. After 24 hours, the number of bacteria was counted.

Antimicrobial durability test method (Water resistance) A test piece was obtained by cutting a sample coated plate into a size of 10 cm × 5 cm. Water was placed in a 1 L beaker at a height of 8 cm, placed in a thermostat at 20 ° C., and the test piece was immersed in the beaker. After 24 hours, the test piece was taken out, dried at room temperature, and a part immersed in water was cut out and examined for antibacterial properties.

(Hot water resistant) 10 cm × 5 cm sample coated plate
What was cut to the size of was used as a test piece. Water was poured into a 1 L beaker at a height of 8 cm, placed in a thermostat at 80 ° C., and the test piece was immersed in the beaker. After 60 minutes, the test piece was taken out and dried at room temperature, and then the dipped part was cut out and examined for antibacterial properties.

(Acid resistance) A test piece was prepared by cutting a sample coated plate into a size of 5 cm × 5 cm. A 10% aqueous hydrochloric acid solution was applied to the surface of the coating film of the test piece, and after 60 minutes, the test piece was washed with water and dried, and then examined for antibacterial properties.

(Alkali resistance) A sample coated plate was 5 cm × 5 c
A piece cut into a size of m was used as a test piece. A 10% aqueous sodium hydroxide solution was applied to the surface of the coating film of the test piece. After 60 minutes, the test piece was washed with water and dried, and then examined for antibacterial properties.

Weathering Test Method After exposing the sample coated plate to a sunshine weather meter for 250 hours, the degree of discoloration of the coated surface was visually evaluated by comparing with the reference coated plate. ◎: no discoloration ：: slight yellowing, but not clearly recognized Δ: clearly yellow

(Production Example 1 of Polymeric Substance) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 485 parts of dimethyl terephthalate, 388 parts of dimethyl isophthalate, and tri-n-sulfodimethylisophthalate were added. -Butyl dodecyl phosphonium salt 16
1 part, 443.3 parts of ethylene glycol, 400.4 parts of neopentyl glycol, and 0.52 part of tetra-n-butyl titanate were charged, and a transesterification reaction was performed at 160 to 220 ° C. for 4 hours. Then fumaric acid 2
After adding 9 parts, the temperature was raised to 200 to 220 ° C. over 1 hour, the pressure of the reaction system was gradually reduced, and the reaction was carried out for 1 hour and 30 minutes at a reduced pressure of 0.2 mmHg to obtain polyester (A-1).
I got The composition of the polyester (A-1) is as shown below.

Dicarboxylic acid component Terephthalic acid 50 mol% Isophthalic acid 40 mol% C12 phosphonium salt 5 mol% Fumaric acid 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol% Seeds shown in Table 1 by the same method. Polyester (A
-2, A-3).

Production Example 1 of Graft Polymer 300 parts of polyester (A-1), 360 parts of methyl ethyl ketone, and 120 parts of isopropyl alcohol were put into a reactor equipped with a stirrer, a thermometer, a reflux device, and a metered addition device, and heated and stirred. The resin was dissolved under reflux. After the resin was completely dissolved, a mixture of 65 parts of acrylic acid and 35 parts of ethyl acrylate, 1.5 parts of octyl mercaptan, and 6 parts of azobisisobutyronitrile were added to 90 parts of methyl ethyl ketone.
And a solution dissolved in a mixture of 30 parts of isopropyl alcohol were added dropwise to the polyester solution over 1.5 hours, and the mixture was further reacted for 3 hours to obtain a graft polymer solution. After the graft polymer solution was cooled to room temperature, 59 parts of triethylamine was added and neutralized, and then 800 parts of ion-exchanged water was added and stirred for 30 minutes. Thereafter, the solvent remaining in the solvent is distilled off by heating, and the aqueous dispersion (B-
1). Polyester (A-2,
A-3) is graft-polymerized to form a graft polymer (B-2,
B-3) was obtained.

Preparation Example 2 of Graft Polymer A method similar to that of Preparation Example 1 except that the amount of acrylic acid was changed to 20 parts and the amount of ethyl acrylate was changed to 10 parts in Preparation Example 1 of the graft polymer. Thus, a graft polymer aqueous dispersion (B-4) was obtained.

Production Method 3 of Graft Polymer Graft polymer was produced in the same manner as in Production Example 1 except that 35 parts of N-methylacrylamide and 65 parts of acrylamide were used as the grafting monomer. A polymer aqueous dispersion (B-5) was obtained.

Preparation Example 4 of Graft Polymer The same procedure as in Preparation Example 1 was repeated except that 15 parts of styrene and 85 parts of vinyl acetate were used as the grafting monomer in Preparation Example 1 of the graft polymer. An aqueous dispersion (B-6) was obtained.

Example 1 For 100 solid parts of the aqueous dispersion (B-1), 40 solid parts of an imino group type benzoguanamine resin (Mycoat 105, manufactured by Mitsui Cyanamid Co.) and 0.4 parts of paratoluenesulfonic acid were used. Parts and 300 parts of isopropyl alcohol. Then, it was applied on a TFS (tin-free steel) plate so that the film thickness after drying became 20 μm, and baked at 200 ° C. for 1 minute to obtain a cured coating film. The properties of this coating film are shown in Table 2.

Comparative Example 1 The same procedure as in Example 1 was carried out except that a polyester resin solution obtained by dissolving the polyester (A-1) in methyl ethyl ketone and isopropyl alcohol was used instead of the aqueous dispersion of the graft polymer. A paint was prepared by the method, and then a cured coating film was obtained. Table 2 shows the properties of the obtained coating films.
It was shown to.

Example 2 In Example 1, the graft polymer aqueous dispersion (B-2) was used.
A coating material was prepared in the same manner as in Example 1 except for using, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Comparative Example 2 In Example 1, the aqueous dispersion of the graft polymer (B-3) was used.
A coating material was prepared in the same manner as in Example 1 except for using, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Example 3 In Example 1, the graft polymer aqueous dispersion (B-4) was used.
A coating material was prepared in the same manner as in Example 1 except for using, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Example 4 In Example 1, the graft polymer aqueous dispersion (B-5) was used.
A coating material was prepared in the same manner as in Example 1 except for using, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Comparative Example 3 In Example 1, the graft polymer aqueous dispersion (B-6) was used.
A coating material was prepared in the same manner as in Example 1 except for using, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

(Production Example 2 of Polymeric Substance) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 436.5 parts of dimethyl terephthalate was added.
436.5 parts of dimethyl isophthalate, 322 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 682 parts of ethylene glycol, and 0.55 part of zinc acetate are charged, and the temperature is raised to 160 to 220 ° C. to produce. The transesterification reaction was performed over 4 hours while distilling off the methanol to the outside of the system. After the transesterification reaction, 55 parts of polyethylene glycol having a molecular weight of 1,000 (manufactured by Nakarai Co., Ltd.), 250 parts of antimony oxide and 0.2 part of trimethyl phosphate were added at 250 ° C.
After adding 8 parts and stirring for 15 minutes, the pressure of the reaction system was gradually reduced, and the mixture was reacted at a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes.
A polyester (A-4) having an intrinsic viscosity η = 0.50 was obtained. The composition of the polyester (A-4) is as shown below.

Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 45 mol% C12 phosphonium salt 10 mol% Diol component Ethylene glycol 98.9 mol% Polyethylene glycol 1.1 mol% Various kinds of polyesters shown in Table 1 by the same method. (A
-5, A-6).

Example 5 20 parts of polyester (A-4) was dissolved in 63 parts of a mixed solvent of toluene / methyl ethyl ketone (8/2), and 2 parts of TMP-modified tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) and A paint was prepared by blending 15 parts of a titanium white pigment (manufactured by Teica Corporation). Then TFS
(Tin free steel) The film thickness after drying on the plate is 20μ
m and baked at 200 ° C. for 1 minute to obtain a cured coating film. The properties of this coating film are shown in Tables 2 and 3.

Comparative Example 4 A coating was prepared in the same manner as in Example 4 except that polyester (A-5) was used in Example 4, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Comparative Example 5 A coating material was prepared in the same manner as in Example 4 except that the polyester (A-6) was used, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

(Production Example 3 of Polymeric Substance) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 436.5 parts of dimethyl terephthalate was added.
388 parts of dimethyl isophthalate, 322 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate, 74 parts of sodium 5-sulfodimethylisophthalate, 443.3 parts of ethylene glycol, 400.4 parts of neopentyl glycol and zinc acetate 0.55 parts were charged, the temperature was raised to 160 to 220 ° C., and transesterification was carried out over 4 hours while distilling off the generated methanol out of the system. After completion of the transesterification reaction, 0.44 part of antimony oxide and 0.28 part of trimethyl phosphate were added, and the mixture was stirred for 15 minutes.
The reaction was carried out at a reduced pressure of 2 mmHg for 1 hour and 30 minutes to obtain a polyester (A-7) having an intrinsic viscosity η = 0.50. The composition of the polyester (A-7) is as shown below.

Dicarboxylic acid component Terephthalic acid 45 mol% Isophthalic acid 40 mol% C12 phosphonium salt 10 mol% 5-Sulfodimethylisophthalic acid sodium 5 mol% Diol component Ethylene glycol 65 mol% Neopentyl glycol 35 mol% The polyesters (A)
-8, A-9).

Example 6 300 parts of polyester (A-7) and 150 parts of n-butyl cellosolve were heated and stirred to form a viscous solution, and 550 parts of water was gradually added with stirring to obtain a solid content of 30 parts.
% Of a homogeneous pale white aqueous dispersion solution was obtained. 10 parts of this aqueous dispersion solution and a commercially available water-based acrylic urethane emulsion-based matting paint (Ales Aqualetan, Kansai Paint Co., Ltd.)
Co., Ltd.) (90 parts). Then, it was applied on a TFS plate so that the film thickness after drying became 20 μm, and dried at room temperature for 7 days to obtain a coating film. The properties of this coating film are shown in Tables 2 and 3.

Comparative Example 6 A coating material was prepared in the same manner as in Example 5 except that the polyester (A-8) was used, and a coating film was obtained. Table 2 shows the properties of the obtained coating film.

Comparative Example 7 A coating material was prepared in the same manner as in Example 5 except that the polyester (A-9) was used in Example 5, and a cured coating film was obtained. Table 2 shows the properties of the obtained coating film.

Example 7 20 parts of polyester (A-6) and 1 part of polyethylene glycol (average molecular weight: 1000) were dissolved in a mixed solvent of methyl ethyl ketone / isopropyl alcohol (3/1), and the mixture was dissolved in TMP-modified tolylene diisocyanate (Coronate L, Japan). A coating was prepared by mixing 2 parts of Polyurethane Co., Ltd.) and 15 parts of titanium white pigment (Taica Co., Ltd.). Then, it was applied on a TFS (tin-free steel) plate so that the film thickness after drying became 20 μm, and baked at 200 ° C. for 10 minutes to obtain a cured coating film. Table 2 shows the properties of the obtained coating film.

Example 8 Polyester resin (Byron 200, Toyobo Co., Ltd.)
15 parts of toluene / methyl ethyl ketone (8/2)
It is dissolved in 63 parts of a mixed solvent, and 1 part of polyethylene glycol (average molecular weight: 1000), 5 parts of tri-n-butyldodecylphosphonium 5-sulfodimethylisophthalate and TMP-modified tolylene diisocyanate (Coronate L, Nippon Polyurethane ( 2 parts) and 15 parts of a titanium white pigment (Taica Co., Ltd.) were blended into a paint, and then applied on a TFS (tin free still) plate so that the film thickness after drying was 20 μm. 10 at 200 ° C
Baking was performed to obtain a cured coating film. Table 2 shows the properties of the obtained coating film.

Example 9 15 parts of polyester (A-8) was dissolved in 63 parts of a mixed solvent of toluene / methyl ethyl ketone (8/2), and 5 parts of
-5 parts of tri-n-butyldodecylphosphonium salt of sulfodimethylisophthalate and TMP-modified tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.)
2 parts, 15 parts of titanium white pigment (Taika Co., Ltd.) were blended to form a paint. Then TFS (Tinfree Still)
Coating on a plate so that the film thickness after drying is 20 μm,
Baking was performed at 00 ° C. for 10 minutes to obtain a cured coating film. Table 2 shows the properties of the obtained coating film.

Comparative Example 8 Polyester resin (Byron 200, Toyobo Co., Ltd.)
20 parts of toluene / methyl ethyl ketone (8/2)
It is dissolved in 63 parts of a mixed solvent, and TMP-modified tolylene diisocyanate (Coronate L, manufactured by Nippon Polyurethane Co., Ltd.)
2 parts, 15 parts of a titanium white pigment (manufactured by Teica Co., Ltd.), and 1.5 parts of a silver / zirconium phosphate antibacterial agent (Novalon, manufactured by Toagosei Co., Ltd.) were mixed to form a paint. Then TF
Film thickness after drying on S (tin free steel) plate is 20
μm and baked at 200 ° C. for 1 minute to obtain a cured coating film. The properties of this coating film are shown in Table 3.

Comparative Example 9 2.5 parts of a silver / zirconium phosphate antibacterial agent (Novalon, manufactured by Toagosei Co., Ltd.) was used. ) 97.5 parts to give a paint. Then, it was applied on a TFS plate so that the film thickness after drying became 20 μm, and dried at room temperature for 7 days to obtain a coating film. The properties of this coating film are shown in Table 3.

[0089]

The antimicrobial coating of the present invention has sufficient antimicrobial activity with a small amount of antimicrobial component, and a coating film using the antimicrobial coating has excellent antimicrobial durability and weather resistance.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

Claims (7)

[Claims] An antibacterial paint containing a phosphonium salt compound and / or a polymer substance containing the phosphonium salt compound, wherein the antibacterial paint contains a hydrophilic substance and / or a polymer containing the hydrophilic substance. An antibacterial paint characterized by containing a substance. 2. An antibacterial paint, wherein the phosphonium salt compound according to claim 1 has a functional group capable of chemically bonding to a polymer substance. 3. The antibacterial paint according to claim 1, wherein the phosphonium salt compound according to claim 1 contains an acidic group and a phosphonium base ionically bonded to the acidic group. 4. An antibacterial paint comprising a polymer in which the phosphonium salt compound according to claim 1 is bonded to a main chain or a side chain. 5. The polymer substance according to claim 1, comprising a dicarboxylic acid component and a glycol component as main components, and
5. The antibacterial property according to claim 4, wherein the copolymer is a copolymerized polyester obtained by copolymerizing a phosphonium salt of a sulfonic acid group-containing bifunctional aromatic compound represented by the formula: 1 to 50 mol%. paint. Embedded image (Wherein A is an aromatic group, X ₁ and X ₂ are ester-forming functional groups, R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups, at least one of which has 10 to 20 carbon atoms.) Alkyl group) 6. An antibacterial paint, wherein the hydrophilic substance according to claim 1 has a functional group capable of chemically bonding to a polymer substance. 7. The method according to claim 1, wherein the phosphonium salt compound and / or the polymer substance containing the phosphonium salt compound and the hydrophilic substance and / or the polymer substance containing the hydrophilic substance are an aqueous solvent and / or an organic solvent. An antibacterial paint characterized by being dispersed or dissolved in a solvent.